Photovoltaic devices with fine-line metallization and methods for manufacture

ABSTRACT

A method for use in forming a photovoltaic device includes forming a doped semiconductor layer on a surface of a semiconductor substrate and forming a metal film on the doped semiconductor layer. A patterned etched resist is formed on the metal film and a dielectric layer is formed on the doped semiconductor layer and the etched resist. A laser having a wavelength absorbable by the patterned etch resist is applied through the dielectric layer to the patterned etch resist to remove the patterned etch resist.

RELATED APPLICATION INFORMATION

This application is a continuation of U.S. Ser. No. 14/707,697 filed onMay 8, 2015, published as U.S. Publication No. US-2016-0329440-A1 onNov. 10, 2016, entitled “Photovoltaic Devices With Fine-LineMetallization and Methods for Manufacture”.

This Application is related to U.S. patent application Ser. No.13/265,462, filed Nov. 15, 2011 (Attorney Docket No. 3304.001A); U.S.patent application Ser. No. 13/637,176, filed Sep. 25, 2012 (AttorneyDocket No. 3304.008A); U.S. Pat. No. 8,236,604, filed Feb. 15, 2011(Attorney Docket No. 3304.010A); U.S. patent application Ser. No.61/589,459, filed on Jan. 23, 2012 (Attorney Docket No. 3304.011(P));U.S. Ser. No 14/373,938, filed Jul. 23, 2014 (Attorney Docket No.3304.011A); U.S. Provisional Patent Application No. 61/657,098, filedJun. 8, 2012 (Attorney Docket No. 3304.012(P)); U.S. Ser. No.61/718,489, filed Oct. 25, 2012 (Attorney Docket No. 3304.013(P)); PCTInternational Application No. PCT/US2013/066532 filed on Oct. 24, 2013(Attorney Docket No. 3304.013AWO), and U.S. patent application Ser. No.14/707,725, filed on May 8, 2015, (Attorney Docket No. 3304.017); whichare incorporated herein by reference in their entirety.

FIELD OF THE INVENTION

Disclosed embodiments generally relate to photovoltaic devices whichinclude solar cells and solar modules containing solar cells. Moreparticularly, the disclosed embodiments relate to improved solar cellstructures and methods of manufacture for increased cell efficiency.

BACKGROUND

Photovoltaic devices convert photons from incident sunlight into useableelectric energy, for example using semiconductor materials depositedover a substrate. The semiconductor layer(s) may be made of an n-typesemiconductor material and a p-type semiconductor material. Theinteraction of an n-type or p-type semiconductor layer with asemiconductor layer of the opposite type creates a p-n junction whichfacilitates movement of electrons and holes created from absorbedphotons via the photovoltaic effect, to produce electric current.

Improved efficiency for photovoltaic conversion, and greater electricaloutput from solar cells/modules, are desired characteristics ofphotovoltaic devices.

Accordingly, a need for a high-efficiency photovoltaic device and amethod of manufacture arises.

SUMMARY OF THE INVENTION

The present invention provides, in a first aspect, a method for use informing a photovoltaic device which includes forming a dopedsemiconductor layer on a surface of a semiconductor substrate andforming a metal film on the doped semiconductor layer. A patternedetched resist is formed on the metal film and a dielectric layer isformed on the doped semiconductor and the etch resist. A laser having awavelength absorbable by the patterned etch resist is applied throughthe dielectric layer to the patterned etch resist to remove thepatterned etch resist.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic, partial cross-sectional view of a solar cell,with an optimized front contact structure for a high-efficiency solarcell;

FIG. 2 shows that a metal contact line may be used as a seed layer tostart plating an electrode to a desired thickness;

FIGS. 3-10 are schematic, partial cross-sectional views of a solar cellshowing an example embodiment of the invention in which a metal etchresist is used to form a metal grid pattern for e.g., a solar cell, asfollows:

FIG. 3 shows the metal contact deposited on a substrate of the cell;

FIG. 4 shows a narrow resist dispensed over the metal film of the cell;

FIG. 5 shows the metal contact etched except for a portion thereofcovered by a resist;

FIG. 6 shows a single, dual-function passivation/antireflection layerformed over the cell of FIG. 5;

FIG. 7 shows a laser removing the resist and a portion of thepassivation/antireflection layer of FIG. 6 to leave the contact andportions of the single, dual-function passivation/antireflection layer;

FIG. 8 shows an electrical contact formed on the remaining metalcontact;

FIG. 9 shows an embodiment of a manufacturing process for forming thedevice of FIGS. 1-8, in flowchart form;

FIG. 10 is a planar view showing an example of an electrodeconfiguration;

FIG. 11 shows a simplified diagram of a laser machining system suitablefor performing the laser processing of the present invention;

FIG. 12 shows an example of two applicable beam intensity power densityor fluence profiles in accordance with the present invention;

FIGS. 13 and 14 show examples of how a square top-hat beam profile maybe scanned or translated over a substrate, in a process for theself-aligned selective laser ablation of dielectric coating overlying apatterned metal film, in accordance with the present invention; and

FIGS. 15 and 16 show examples of how a square top-hat beam profile maybe scanned or translated over a substrate, in a process for theself-aligned selective laser ablation of dielectric coating overlying apatterned metal film, in accordance with the present invention.

DETAILED DESCRIPTION

Aspects of the present invention and certain features, advantages, anddetails thereof, are explained more fully below with reference to thenon-limiting embodiments illustrated in the accompanying drawings.Descriptions of well-known materials, fabrication tools, processingtechniques, etc., are omitted so as to not unnecessarily obscure theinvention in detail. It should be understood, however, that the detaileddescription and the specific examples, while indicating embodiments ofthe invention, are given by way of illustration only, and are not by wayof limitation. Various substitutions, modifications, additions, and/orarrangements within the spirit and/or scope of the underlying inventiveconcepts will be apparent to those skilled in the art from thisdisclosure.

The disclosed embodiments are directed to photovoltaic devices,including photovoltaic cells and modules containing a plurality ofphotovoltaic cells, and method for their manufacture. The photovoltaiccells can be used as monofacial cells which receive light at one surfaceor as bifacial cells which can receive light from the one surface andfrom an opposite surface.

An important parameter which affects the efficiency and output of asolar cell is an amount of area on a light-incident surface of the solarcell which is covered (directly) or shaded (by an angle of incidentsunlight) by electrodes which are required to collect and moveelectrical current which is generated by the solar cells. The coveredarea and shading from electrodes may be reduced by decreasing the sizeof the electrodes. For example, electrodes are often formed as fingers,and decreasing the width of the electrode fingers increases thephotoactive area available on the device for receiving and convertingincident light.

In one example, conventional solar cell production may use screenprinting technology to print electrodes on a front surface of aphotovoltaic device with such a technique often using a metal paste(e.g., silver paste). This technique may result in a comparatively broadelectrode line width (e.g., in excess of 50 um (typically about 100um)), and a fairly low line conductivity of the metal grid due to theuse of several non-metallic components (e.g., glass frit) in the printedpaste. As indicated above, increased line width may result in increasedshading and less light falling on the light-incident surface of thesolar cell. In addition, a firing process may result in contamination ofa substrate of the cell by ingredients of the metal paste, therebyreducing the energy conversion efficiency of the device. Moreover, somemetal pastes (e.g., silver) may be comparatively expensive making themunfavorable as a primary electrode material.

FIGS. 3-16 show an example embodiment of the invention which uses ametal etch resist to form a metal grid pattern for e.g., a solar cell.It is understood that many techniques exist for the formation of a metalpatterns on a substrate in accordance with the invention and that thesequence presented is only one possible example.

Initially, a substrate 1 is supplied. This substrate may be a siliconsemiconductor wafer of either p or n-type doping. The substrate may betextured, for example with a random pyramid pattern to improve lighttrapping in the solar cell. The substrate may have dopant diffusions oneither or both sides to form emitter structures or surface fields. Suchdopant diffusions may be patterned, for example to form so-calledselective emitter structures. The substrate may have thin filmpassivation layers present on either or both surfaces. Such passivationlayers may for example consist of doped or intrinsic amorphous siliconlayers, silicon dioxide, silicon nitride, doped or intrinsicpoly-silicon, doped or intrinsic silicon carbide, aluminum oxide or anyof a large variety of such passivation layers and combinations thereof.

A metal film 4 is deposited over a surface of the substrate, and thestructure shown in FIG. 3 results, which shows a metal film 4 oversubstrate 1. Such metal deposition may, for example, be performed usingwell established techniques such as sputtering, thermal evaporation ore-beam evaporation. It is understood that this metal film may consist ofmultiple different metal layers where these metal layers are required toperform different functions. For example, a bottom—next to thesubstrate—metal layer may be required to form good electrical contactand adhesion to the substrate, a top or middle metal layer may berequired to act as a diffusion barrier, and a top metal layer may needto function as an electroplating seed. Further, it is understood thatthe metal film may require specific properties, for example thicknessand/or composition.

A patterned etch resist 3 (e.g., narrow resist line) may next be formed(e.g., using an ink jet printer) over metal film 4 to form a structure155 as depicted in FIG. 4 and indicated as Step 307 in FIG. 9. Patternedetch resist 3 may be formed from well-known materials, such ascommercially available inkjet printable resists configured to absorb awavelength of a laser light source, and to be deposited in a pattern onmetal film 4 of structure 155. In one embodiment, a resist pattern mayinclude a pattern for later forming narrow conductive fingers and widerconnective bus-bars extending transversely to the fingers. In oneexample, resist 3 may be a UV curable black or other colored ink resistwhich may absorb the wavelength of a laser light source. Before applyingresist 3 (e.g., via printing), structure 155 depicted in FIG. 3 may bepretreated to reduce a surface energy of the metal film 4, making it ahydrophobic surface. Such pretreatment helps ensure that when the resistis applied (e.g., printed) the resist beads up on metal film 4 and doesnot spread out. The pretreatment may include a deposition of a monomerwith a hydrophobic group with reactive chains which attach to a surfaceof metal film 4. Alternatively, a plasma treatment may be used for suchpretreatment, or a monomer layer of molecules may be deposited as thesurface treatment. In short, any surface treatment of metal film 4 whichmakes the surface hydrophobic or otherwise inhibits flow of a resist(e.g., resist 3) on a metal film (e.g., metal film 4) may be used.Resist 3 (FIG. 5) may be formed by any of various well-known techniques.In one embodiment, resist 3 (FIG. 4) may be formed by inkjet printing asindicated above. In another embodiment resist 3 (FIG. 4) may be formedby dispensing, spraying, screen printing or photolithographictechniques.

After resist 3 is printed on metal film 4, resist 3 on metal film 4 maybe cured under UV light to pin resist 3 in position on metal film 4.Depending upon the particular resist material that is selected or used,it could be advantageous to use a low temperature curing process in therange of 70-150 C to drive out residual water, if present, from theresist and promote adhesion to the metal layer. After resist 3 is cured,metal film 4 may be etched. Patterned etch resist 3 protects portions ofmetal film 4 which are covered by patterned etch resist 3 duringexposure of metal film 4 to a suitable metal etch solution, such as anacid solution (e.g., via a suitable metal acid etch solution, in step308 of FIG. 9).

Etching of metal film 4 produces a structure 160, as shown in FIG. 5,which shows no undercutting of metal film 4 beneath the resist. However,depending on the etch conditions, the etching may provide a slightundercutting of metal film 4 beneath resist 3. In an example of metalfilm 4 being formed of a titanium and nickel/vanadium seed layer atwo-step etch can be used. Nitric acid or iron chloride may be used toetch the nickel/vanadium layer and a hydrofluoric acid etch may be usedto etch the titanium layer. Other etching solutions may also be useddepending on the materials forming the resist (e.g., resist 3) and metalfilm (e.g, metal film 4).

A material layer 212 which functions both as a passivation layer andantireflection coating, may next be formed on a front surface 162 on astructure 164, as depicted in FIG. 6 and indicated in Step 309 of FIG.9. Alternatively, such a material layer (e.g., material layer 212) couldbe formed on surface 162 and a back surface (not shown) of substrate 1.The material layer could be formed of any dielectric material which hasoptical properties of an anti-reflective coating and can passivatesubstrate 1 and may be deposited using PECVD. As also shown in FIG. 6,material layer 212 (e.g., a dual-function passivation/antireflectionlayer) is deposited over any exposed etch resist (e.g., etch resist 3)and over substrate 1. Although FIG. 6 is not to scale and enlarged forclarity, it is understood that material layer 212 coats texturedsurfaces of substrate 1 while maintaining a texture pattern, i.e.,material layer 212 retains the texture after deposition of materiallayer 212. Material layer 212 could be formed of silicon nitride whichwould allow the layer to act as a passivation layer and antireflectioncoating. Further, material layer 212 may also be formed of an undopedlayer of silicon carbide (e.g., as an anti-reflection coating and as apassivation layer). In another embodiment (not shown), a material layermay be applied as described above but which would not perform bothantireflection and passivating functions. For example, titanium oxidemay be utilized as such a layer which provides an anti-reflectioncoating only.

After material layer 212 is applied, etch resist 3 and a portion 212 a(FIG. 6) of material layer 212 over etch resist 3 may be removed asdepicted in FIG. 7 and indicated in Step 310 of FIG. 9. Such removal maybe performed via any of various methods which breaks, dissociates, orotherwise allows portion 212 a and a portion of resist 3 to be removedfrom a surface 264 of metal film 4.

In one embodiment, the described removal may be accomplished with alaser 260, as shown in FIG. 7. For example, a laser beam 262 (FIG. 7)emitted by laser 260 may have a wavelength which is configured to heatand expand the patterned etch resist (e.g., etch resist 3), while noneof the other materials or components of the device are significantlyaffected. Because laser beam 262 (FIG. 7) interacts with patterned etchresist 3 (FIG. 6) only, the laser beam is considered to be self-alignedto resist 3 (FIG. 6).

More specifically, laser 260 may emit a laser beam 262 (or multiplelaser beams 262) having a wavelength which passes through portion 212 aof material layer 212 remaining over resist 3 and which is absorbed byetch resist 3. Irradiation by laser 260 may thus heat resist 3 causingit to expand, crumble and dissociate from surface 264 of metal film 4while the other materials or components of the device are notsignificantly affected. Portion 212 a overlying resist 3 may be brittle,and thus the laser may cause portion 212 a to break apart and flake off.Any portion of the laser beam which passes through resist 3 may alsoreflect off surfaces 264 of the metal film 4 and back into resist 3further facilitating heating of resist 3. The surfaces of substrate 11(FIG. 7) may be completely irradiated by the laser at the same time,progressively, or in portions corresponding to the locations ofpatterned etch resist 3 (FIG. 1G), for example.

As indicated, laser 260 may emit laser beam 262 which may have awavelength which interacts preferably with patterned etch resist 3,causing patterned etch resist 3 to crumble and portion 212 a of thematerial layer 212 overlying the etch resist to break apart and flake,resulting in an ablated structure 170 as shown in FIG. 7. Structure 170may be completely irradiated by the laser at the same time,progressively, or in portions corresponding to the locations of resist 3(FIG. 6), for example. Laser 260 may be a 1064 nm laser, for example.During use, the laser may scan a surface (e.g., portion 212 a) withrectangular laser spots forming a laser beam (e.g., laser beam 262)having a size of about 2×2 mm without an overlap of the rectangles. Asmall gap up to 50 microns (um) may exist between such rectangle(s) toavoid the laser beam (e.g., laser beam 262) hitting a spot twice. Afterthe resist (e.g., resist 3) is removed, any contact by the laser beam(e.g., laser beam 262) with an underlying portion (e.g., metal film 4)may be detrimental to such underlying portion such that it is desirableto avoid multiple applications of the laser at a particular location andto avoid the laser beam contacting the metal film after removal of theresist.

Further, although the process is described relative to structure 155,the process of forming a metal film (e.g., metal film 4), forming anetch resist (e.g., etch resist 3) on the metal film, forming adielectric layer (e.g., material layer 212 forming an antireflectionand/or passivation layers) and utilizing a laser to remove a portion ofthe resist may also be utilized on other solar cell structures havingsubstrates formed differently than that described relative to structure155.

FIG. 11 shows a simplified diagram of a laser machining system suitablefor performing the laser processing in accordance with the presentinvention. Laser beam 262 may be generated in laser 260. The laser beamis fed through optional external optics which may include componentssuch as a beam expander, beam collimator, beam homogenizer, imaged mask,fiber beam delivery system, variable attenuator, relay lenses andmirrors. A galvanometer scanner and/or a translation stage may be usedto translate the laser beam to cover the substrate e.g., for a solarcell. The final lens is used to focus the beam onto the substrate e.g.,for a solar cell. Such a laser machining system arrangement, asillustrated in FIG. 11, is readily available and applicable to highthroughput industrial applications such as solar cell manufacturing.

This invention may use different laser beam intensity profiles. FIG. 12shows an example of two applicable beam intensity (power density orfluence) profiles.

A Gaussian beam profile, or close to Gaussian, is one typicallygenerated by many laser sources, the intensity distribution in anytransverse plane is a circularly symmetric Gaussian function centeredabout the beam axis. An alternative beam profile shown is the so-called“Top-Hat” or “Flat-Top” beam profile. Such a profile ideally has anear-uniform intensity within the exposure area. The Top-Hat exposurearea shape may be circular, square, rectangular or any shape generatedby appropriate optics. Such a Top-Hat beam profile is typicallygenerated using special diffractive or refractive optics, or multimodefibers, called beam shapers. Either of these profiles or combinations orvariations thereof may be used for laser processing according to thepresent invention.

FIGS. 13-14 show examples of how a square top-hat beam profile may bescanned or translated over a substrate, in a process for theself-aligned selective laser ablation of dielectric coating overlyingmetal film 4. As can be seen, this process is tolerant to variations inthe size, placement and shape of the narrow metal fingers. It isunderstood that a variety of different beam scanning, overlap andplacement schemes are applicable to this invention and that the twoshown are only representative examples of the general principle.

FIGS. 13-14 show an example of full area laser irradiation using asquare top-hat profile laser beam spot. The square spot is scanned ortranslated to cover the entire process area. As can be seen from FIG.14, for a self-aligned selective laser ablation process removing adielectric coating overlying etch resist 3 on metal film 4, thisirradiation pattern functions irrespective of the size, position orshape of etch resist 3.

FIGS. 15-16 show an example of aligned laser irradiation pattern using asquare top-hat profile laser beam spot. The square spot is scanned ortranslated to cover metal film 4 (e.g., narrow metal fingers). As can beseen from FIG. 16, for a selective laser ablation process removing adielectric coating overlying etch resist 3, this irradiation patterndoes not need to accurately track variations in the size, position orshape of etch resist 3.

Any debris associated with the breakdown of resist 3 and overlyingportion 212a of material layer 212 may be removed for example, byblowing any debris away using a suitable blower as indicated, forexample, in Step 311 of FIG. 9. A water-based detergent or solvent-basedspray may optionally further be used to clean structure 170 depicted inFIG. 7.

Following the cleaning of structure 170 described above and depicted inFIG. 7, a low temperature anneal may be conducted with a relatively lowtemperature of less than or about 500° C. to promote adhesion of metalfilm 4 to substrate 1 and a good electrical contact as indicated in Step312 of FIG. 9. This anneal can be done, for example, in a temperaturerange of about 250° C. to about 500° C. As one specific example, theanneal can be accomplished at a temperature of about 375° C. for about 2minutes. This low temperature anneal can also reduce defect damage tothe semiconductor layers of substrate 1 which may have occurred duringdeposition of metal film 4. The anneal may be conducted in an atmospherehaving a very low concentration of oxygen to avoid oxidation of surface264 which might make it hard to later electroplate. Typically, theatmosphere will contain less than 100 ppm of oxygen, and preferably lessthan 20 ppm of oxygen. The anneal atmosphere can be a nitrogenatmosphere (N2) with a small amount of a forming gas, such as hydrogen.The forming gas utilized may be dependent upon a type of material/metalbeing used (e.g., metal film 4) to avoid oxidation or other un-desirablecharacteristics of such material/metal. The forming gas may be in aconcentration of about 0 to about 5% by volume, for example, 4%. Theforming gas may further help reduce oxidation of surface 264.

As shown in FIG. 8, a conductor 270 may next be formed on metal surface264. Conductor 270 may be formed from one or a plurality of conductivematerials, for example metals such as nickel, copper, silver, titanium,vanadium, tin or any combination thereof. The conductor may be appliedto surface 264.

In one embodiment, conductor 270 may include a metal stack comprising alayer of nickel applied to surface 264, a layer of copper electroplatedto the layer of nickel, and a layer of silver electroplated to the layerof copper as indicated, for example, in Step 313 of FIG. 9. Conductors270 may be formed by electroplating on the seed metal surface. Theelectroplating occurs on all exposed surfaces (e.g., surface 264) of themetal film 4 (i.e., not on areas of material layer 212). Accordingly,any undercutting of the metal film 4 which may have occurred duringetching of the metal film 4 (FIG. 5) described above may be filledduring the plating process (not shown). An electroless deposition mayalso be used to produce conductors 270. In an example, conductor 270 maybe formed of a nickel, copper, silver conductor stack. A nickel portion271, a copper layer portion 272, and a silver portion may be isotropicplated onto conductor 270.

Using the techniques described above very narrow finger and bus barconductors may be produced. For example, conductive fingers 290 and busbars 292 may be formed as described above for conductor 270. As shown inFIG. 10, conductive fingers 290 may have a width in a range of about 40um to about 60 um and a height in a range of about 5 um to about 20 umand may be spaced on a pitch in a range of about 0.2 mm to about 2.5 mm.Transverse bus bars 292 may have a width in a range of about 0.5 mm toabout 2.5 mm, a height in a range of about 5 um to about 20 um and maybe spaced from one another by about 52 mm. Finger conductors 290 and busbar conductors 292 allow more light into a substrate (e.g., substrate 1)for photo conversion and the short height described reduces shading oflight hitting such a substrate.

A number of embodiments have been described and illustrated.Nevertheless, it will be understood that various modifications may bemade without departing from the spirit and scope of the invention, whichis defined solely by the scope of the appended claims.

1. A method for use in forming a photovoltaic device, comprising:forming a metal film on the doped semiconductor; forming a patternedetch resist on the metal film; etching the metal film to form a metalgrid pattern; forming a dielectric layer on the doped semiconductor andthe etch resist such that a first portion of the dielectric layer isdirectly on the etch resist and a second portion of the dielectric layeris directly on the doped semiconductor; and applying a laser to thepatterned etch resist through the dielectric layer to remove thepatterned etch resist and the first portion of the dielectric layer. 2.The method of claim 1 wherein the etching the metal film to form thegrid pattern comprises etching the metal film to form the metal gridpattern for a plurality of bus bars and a plurality of conductivefingers for the photovoltaic device.
 3. The method of claim 1 whereinthe forming the dielectric layer comprises forming the dielectric layerwhile retaining a texture pattern of the doped semiconductor.
 4. Themethod of claim 1 wherein the applying the laser comprises applying thelaser using full-area patterning.
 5. The method of claim 1 furthercomprising pretreating the metal film prior to the forming of thepatterned etch resist to make the metal film hydrophobic.
 6. The methodof claim 1 wherein the forming the etch resist further comprises curingthe etch resist to pin the etch resist in a position on the seed metallayer.
 7. The method of claim 1, further comprising annealing the metalfilm after the patterned etch resist and the portion of the layer areremoved.
 8. The method of claim 7, wherein the anneal is conducted at atemperature less than 500° C.
 9. The method of claim 8, wherein theanneal is conducted at a temperature in the range of about 250° C. toabout 500° C.
 10. The method of claim 7, wherein the anneal is conductedfor about 5 minutes.
 11. The method of claim 1, further comprisingforming a conductor on the metal film to form a plurality of bus barsand a plurality of conductive fingers by electroplating.
 12. The methodof claim 11 wherein the forming the conductor comprises repairing anundercut in the seed metal layer.
 13. The method of claim 11, whereinthe conductor is formed by electroless deposition.
 14. The method ofclaim 11, wherein the conductor is formed by an electroplated sequentialdeposition of nickel, copper and silver.
 15. The method of claim 1,wherein the laser has a wavelength of about 1064 nm absorbable by thepatterned etch resist.
 16. The method of claim 1, wherein the laser beamcomprises a plurality of non-overlapping laser spots.
 17. The method ofclaim 1, wherein the laser spots are spaced from each other by up to 50micrometers.
 18. The method of claim 1, wherein the forming thedielectric layer comprises forming an antireflection layer or apassivation layer.